Sulphides of alkylated aryl, oxyorganic carboxylic acids



' UNI-I150;v STAT summons or Arxmrnp ARYL, 0x,

I pounds or condensation products which are solimproved.

of oil miscible compounds these alkyl' substituents preferably contain at least twenty carbon 'M-an Patented Aug. 7, 1945 ES i- PATENT; OFFlCE oaoamc caanoxmc ACIDS Orland M. neim'wooabm, N. 1., assirnorto SolWo Drawing.

copy-Vacuum Oil Company, Incorporated, a corporation of New York a,

Application December 17, 1942, Serial N0. 469,361

12 Claims. (01. zoo- 516) 1 ins within such general classification those comuble or miscible with mineral oil. I

My, invention is predicated upon the discovery that the oil-miscible compounds or condensa- -'tion products contemplated herein when blended with a viscous mineral oil fraction such as a hy-' drocarbon lubricating oil, will improvevarious properties of the oil. For example, I have found that the compounds or reaction products contemplated herein will inhibit oxidation of the oil, thereby retarding the formation of sludge anti acidic'products. They also have a peptizing action on such sludge as may be present or as may eventually be formed. Thus, any one of these preferred oil-miscible compounds or condensatemal combustion engine lubricants 'to retard or prevent the stickingof piston rings, the clog ging of piston ring slots, the corromon of bearlugs and other parts susceptible to attack-'by' acidic products of oxidation in the oil, and through a proper choiee'of metal substituent (lead, copper, tin or nine, for example) the loadca ryinsrability or lubricity 0f the Oil be .The alkyl substituents on the aryl'nuclei of the compounds or condensation products contemplated herein act to impart oil-miscibility to the product and for the preferred genefal class atoms. This preferred sub-group of compounds having the so-called "heavy alkylf groupsof at least twenty carbon atoms '(such as-derived, for

example, from a FriedeI-Y-Crafts condensation with chlorinated paraflln wax) act to improve the oil in the same respects notedabove, and, in addi-- tion, they improve the viscosity index and pour point of the oil. A petroleum wax such as pa ailln wax constitutesa preferred source for these I tlon products may, for example, be usedin inso-calledheavy alkyl substituents of the latter type and for that re'ason'the. preferred multifunctional. compounds may be hereinafter designated asfwax-substituted. .It is to be understood, however, that the term wax as used in this regard is not'restricted to substituent groups a derived from petroleum wax but is intended to include substituent groups derived fromany aliphatic hydrocarbon or mixture thereof or any. predominantly aliphatic material which is in character or constituents similar to theconstit- -uents of petroleum wax.

i It is to be understood that the present invention isnot concerned with mineral oil'compositions, such compositions forming the subject matter of my. copending. applicati'onSerialNo. 330,693, filed April 20, 1940, now Patent 2,326,496

issued August 10, 1943, of which the present application is a cOntInu'ation-in partand to which .20 reference is made for further details in the comw position of these compounds or reaction products.

It is also'to beunderstood that the present invention is not confined to the oil-miscible or toil-soluble compounds and that the use of the' preferred oil-miscible compounds is not confined to the improvement of mineral oils, since this whole class of new materials is possessed of i valuable properties irrespective of oil-miscibility.

' For example, thecompounds or condensation the compounds 'or compositions are possessed of valuable pharmaceutical, insecticidal or similar properties. Numerous other uses and applications of the compounds or condensation products contemplated herein will readily apparent to those skilled in the art from the following description of their'compositions and a typical .method'for synthesizing them.

, In the aforesaid copendingapplication, which is directed tomineral oil compositions having incorporated therein the compounds or composi-' tions of the present invention, 1- have distinguished over the chemical compounds or compositions described in Patent 2,198,293, in which I am a co-inventor. Briefly, the compounds or i compositions of said patent are anal-substituted aryl ether acids; whereasthe compounds or compositions of the present invention are sulproducts contemplated hereinmay be used as intermediates in the production of resins, resin-'- like materials, rubber substitutes, etc. Certain of phides, selenides or tellurides of alkyl-substituted aryl ether acids wherein at least two of said aryl ether acid groups are interconnected by at least one atom of sulphur, selenium or tellurium. Thus, a typical compound or condensation product of the type contemplated herein may be represented by the general formula:

wherein Y represents an element selected from the group consisting of sulphur, selenium and tellurium; n represents a whole number from one to four; -O-Z-COOH represents an ether carboxylic acid group (or, oxy-organic carboxylic acid group) in which- Z represents an aliphatic, alicyclic or aromatic group; R and R represent aliphatic hydrocarbon groups containing at least twenty carbon atoms; and a: representsa whole number from one to four. It will be noted that this compound is a condensation product of an alkyl-substituted aryl ether acid in which at least one alkyl group (R) is attached to an aryl nucleus and in which an ether acid group is attached to the aryl nucleus through the ether oxygen atom.

It is to be understood, of course, that the aryl nucleus (disclosed in the general formula above as a substituted phenyl group) may be either monoor poly-cyclic; also that it may carry' other substituents, such as ester, keto, alkoxy, alkyl sulphide, aryl sulphide, halogen, hydroi'ry, amino, nitro, etc., as more fully disclosed in application Serial No. 330,693, or which this is a continuation-in-part. It will be apparent that when the aryl nucleus is poly-cyclic, a: may be greater than 4 inasmuch as there are a greater number of replaceable hydrogen atoms than in a phenyl group.

As indicated above, Z may be an aromatic nucleus, and in th'at event, this aryl nucleus may have R and R substituents, and also the various substituents referred to above, the condensation with the linkage (Y) a may take place between the aryl nucleus or nuclei of such Z group, The foregoing general formula is intended to include such modified derivatives. When Z is aliphatic, certain of the various substituents (exclusive of those of strictly aromatic origin) referred to above may be present therein.

obtained by the latter method are or lighter color than those obtained by the first method and for this reason, the latter method is preferred. Still another desirable procedure consists in converthereof; and if a mixture of sulphur halides is used, the condensation products will be a mixture of sulphides. Monosulphide condensation products are obtained when elementary sulphur is used in place'of a sulphur dihalide, but this is not con 7 sidered the most desirable procedure. sulphides of higher sulphur content can be formed by reacting a condensation product having the disulphide linkage with elementary sulphur or with an alkali polysulphide or with an alkyl vtetrasulphide. Such higher. sulphur derivatives may also be obtained by first reducing the disulphide to form the corresponding th'lophenol or aryl mercaptan of the 'alkylated aryl ether acid and then reacting the latter with sulphur dichloride (to form the trisulphide) or with sulphur monochloride (to form the tetrasulphide).

The alkylated aryl ether acids and their alkali metal salts used in preparing the sulphides may be obtained in various ways. The details'in desirable procedures for preparing the alkylated aryl ether acids are described in Patent 2,198,293 referred to above. A typical procedure for preparing It is to be understood that the term sulphide, I

as used herein, is inclusive of the monosulphides,' disulphides, trisulphides, tetrasulphides, etc. that is, it includes both monosulphides and polysulphides and is alsoinclusive of such polymers and related complex derivatives as may be formed by the procedures described hereinafter. It is to be further understood that the terms: selenides and tellurides have similar connotations.

As the sulphur derivatives or sulphides of the alkylated aryl ether acids are the preferred class of condensation products contemplated herein,

' the invention will be specifically described in connection with these derivatives, although','as aforesaid, the selenide and telluride derivatives are contemplated as coming within the scope of 'the broad inventive concept.

Several general procedures for synthesizing the sulphides of alkylated aryl ether acids may be employed. An alkylated aryl ether acid may be reactedwith a sulphur halide, or an alkali metal carboxylate of an! alkylated aryl ether acid may be reacted with a sulphur halide. The sulphides the alkali-carboxylates and the corresponding alkylated aryl ether acids is described hereinafter.

Examples of halogenated organic carboxylic acids which may be used (as their alkali metal salts) in the formation of aryl ether acid derivatives are the halogenated monobasic aliphatic acids such as acetic, butyric, octoic, palmitic.

stearic, naphthenic, etc.; polybasic acids'such as maleic, succinic, adipic, etc.; and aromatic acids such as benzoic, phthalic, cinnamic, furolc, etc. Both aliphatic and aromatic acids may also carry substltuents such, for example, as keto, nitro, amino, hydroxy groups and the like.

The alkylation of the aromatic compound may be carried out in various ways. A preferred procedure is to subject a hydroxyaromatic compound to a Friedel-Crafts condensation reaction with a halogenated aliphatic hydrocarbon, which, for obtaining the preferred mum-functional addition agents, should be an aliphatic hydrocarbon containing at least twenty carbon atoms or a mixture of aliphatic hydrocarbons predominantly comprised of compounds having at least twenty carbon atoms. This alkylation may also be carried out with unsaturated hydrocarbons or aliphatic alcohols, using sulphuric acid or anhydrous aluminum chloride as a catalyst. In alkylating phenols with high molecular weight alcohols, however, it is preferred to convert the alcohol to the corresponding halide (or polyh'allde) and then condense the alkyl halide with'the hydroxyaromatic compound by the Friedel-Crafts reaction.- For obtaining the preferred multi-functional addition agentwith unsaturated hydrocarbons or aliphatic alcohols, they should be high molecular weight compounds containing at least twenty carbon atoms, such, for example, as eicosylcne, carotene,

obtaining the. alkylated hydroxyaromatic compound, and, ass, source of the allgvl substituent,

- weight hydrocarbons typified by those which charpoly-cyclic and monoor-poly-hydric hydroxypreference is given to mixed high molecular or melting point not substantiallyless than about 120 F. which is predominantly comprised of aliphatic hydrocarbons having a molecular weight of at least 250 and containing'at least twenty carbon atoms. 1

Hydroxyaromatic compounds which may be used in the alkylation reaction are monoand aromatic compounds which may or may not be otherwise substituted. Specific examples of such compounds are:.phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxy-diphenyl, benzylphenol, phenyl .ethyl phenol, phenol resins, methyl hydroxy-diphenyl, alpha-andbeta-naphthol, tolyl naphthol, anthrol and the like, with special preference given to phenol and alphaand beta-naphthol. 7

Where. it is desired to obtain a compound or condensation product in which the aryl nucleus contains inaddition to one or more alkyl groups (R and "R') or an. ether acid group 'O-Z-COOH) another substituent in addition to 3 or in place of residual hydrogen, it is pointed out that with the exception of substituents such as aralkyl, aryl alkaryl, halogen, hydroxyl and aroxy, such substituen t groups are introduced after 40 the mixture was stirred at 500 E during a alkylation and generally before introduction of the ether acid group. The usual methods for the introduction of these substituents'into non-alkylated hydroxyaromatic-compounds may be employed in connection with the alkylated or wax-substituted hydroxyaromatic compounds contemplated here- I in.- Methods for the introduction of such substitoms In this preferred class of compounds sped c preference is given to the condensation prod not, which was approximately a one-fourth blend ucts derived from alkyl-substituted hydroxyaromatic compounds in which the alkyl substituent is derivedfrom petroleum wax.- The details in atypical procedure for synthesizing these socalled wax-substituted hydroxyaromatic compounds (wax-phenol) are'described in my Pat- ,ent'2,19'l,833. Briefly, this. procedure involves reacting a' chlorinated wax, such as chlorinated paraflinwax, with a phenolinthe presence of a Friedel-Crafts catalyst at elevated temperature. The

chlorinated wax should have a chlorine content of from about 10 per cent to about 16 per cent,

' andithe reaction mixture may contain'about three atomic proportions of chlorine (in a chlorwax of 16 per. cent chlorine content) to one molecular proportion ofphenol. A waxpheno obtained irom such a reaction mixture may be designated "as'wax-phenol (3-16). Parenthetical express ons of the type (A'-B) will be used hereinafter in connection with the wax-substituted derivatives to" designate: (a) the number of atomic propor- N s,s s1i,aa4 melene; polymerized isobutylene, etc.,'- and myricyl 4 alcohol, ceryl alcohol. etc. 1

The Friedel-Crafts synthesis is preferred for 3 as, of chlorine in the chlorinated wax reacted withone mol of hydroxyaromatic compound, and

(B) chlorine content of the chlorinated wax. In the hove example, A 3 andiB 16. The

5 same designation will also apply to the sulphides of the wax-aroxy organic carboxylic acids which constitute the ultimate product derived from the wax-phenol.

Illustrative procedures which may be followed 1 in preparing the sulphides of alkyd-substituted aryl ether acids contemplated herein are given in 5 (b) Procedurei Wax sodium phenate (3-16) was prepared by reacting wax-phenol (3-16), obtained according to the procedure outlined in my Patent 2,197,833,

0 with sodium butylate at about 300 F. and dis- ,tilling oil the alcohol.

A solution'of l2.'7.5 grams of monochloracetio.

acid in cc. of anhydrous alcohol was converted to sodium chloracetate by adding thereto a standard alcohol solution of sodium hydroxide, main- This sodium chloracetate mixture was then added to a solution of 200 grams of the wax sodium phe-' nate (3-16) in 600 grams of the mineral oil and hour period to form the wax-substituted phenoxy sodium acetate. The. temperature was then lowered to about 100 F. and the mixture was sulphurized by adding, with rapid stirring,- 19.7 grams of 45 sulphur monochloride at a rate sufliciently slow to avoid appreciable rise in temperature of the mixture by the heat of reaction developed. The mixture was then stirred at this temperature for about one hourto complete-the sulphurization,

followed by distilling off the alcohol and waterwashing the mixture until the aqueous extract was neutral. All traces of alcohol and water were then removed bysteam-tIeating the mixture at about 300 F. to obtain the finished prodin mineral oil.

The pure di(wax-phenoxy acetic acid) disulphide is obtained in the free condition (rather than in a mineral oil blend) by using a light boil.- ing distillate such as Stoddards Solvent as the diluent in place of mineral oil, and following the foregoing procedure andflnally distilling on? said light boiling distillate.

[Exam'emll Breparation of dflwax-phenomy benzoic acid) j disulphide -(a) Reaction mixture! Brom sodium benzoateg (BrCsHrCOOH) "grams" 29 Wax sodium phenate .'-do'. 100- Mineral oil of Sgt). V. of 67 Y 4 secs. @2 0" F do- 300 Sulphur monochloride .--do 9.8

taining the reaction temperature at about 100 F.

' acted brom sodium benzoate.

diluted with 109 cc. of chlorbenzene, and the sulphurization was carried out by adding 9.8

(b) Procedure:

'A solution of 100 grams of wax sodium phenate (obtained as in Example I (b)) in 300 grams-of the mineral oil was mixed with 29 grams of brom sodium benzoate and stirred at a reaction temperature of about 400KB. during a four-hour period with copper powder as catalyst, to form the disodium salt of (wax-phenoxy benzoic acid).

The reaction mixture was then filtered to remove sodium bromide, copper powder, and any unre- Tlie filtrate .Lwas

grams of sulphur monochloride at 100 F. at a rate sufficiently slow to avoid appreciable temperature rise by the heat of reaction, and stirring one hour at the temperature to complete the sulphurization, whereby the di(wax-phenoxy benzoic acid) disulphide is formed. The product was purified by water-washing the mixture'until the aqueous extract was neutral, followed by distilling oii the chlorbenzene diluent to obtain the finished product, which was approximately a one-fourth blend in mineral oil. i

As indicated above in Example I (b), the pure di(wax-phenoxy benzoic acid) disulphide is obtained in the free condition by replacing the mineral oil used above as a diluent with a light boil- .ing diluent such as, for example, Stoddards Solvent, and following the procedure outlined above and finally distilling of! said light boiling distil-- ate.

It will be understood that when a mixture of aliphatic hydrocarbon compounds, such as petroleum wax, for example, is used as the source of the alkyl substituents, the resulting. composition will be an intimate mixture of compounds or sulphides of alkyl-substituted aryl ether acids,.

which compounds difier from each other with respect to the nature of the alkyl substituent. In other words, where the alkylation of the aryl nucleus has been effected with a mixture of aliphatic hydrocarbons, the resulting product will likewise be a mixture of compounds differing with respect to the alkyl substituent-but having in common the same ether acid group (O-Z-COOH) and the samecharacterizing aryl nucleus discussed above.

Compounds or condensation products of both the oil-miscible and non-miscible types have been prepared, and of the oil-miscible products which have been tested in mineral oil compositions all have eflected improvement in the properties of the oil. The following examples are illustrative of the "various oil-miscible sulphides of wax-sub- 4 sizingthe. products contemplated by this invention and have listed a number 01' illustrative com- 1. As a new composition pounds or condensation products which are typical thereof, the invention is not limited to the particular procedures or products but includes within its scope such changes and modifications as fairly come within the spirit of the appended claims.

I claim: 1

of matter, a condensation product having the general formula:

uooc-z-o o-z-ooou in which n represents the number of sulphur atoms and is a whole number from 1 to s; O-Z-COOH represents an city-organic carboxylic acid group in which Z is selected from the group of organic groups consisting of aliphatic, alicyclic and aromatic groups; R and R represent aliphatic hydrocarbon groups containing at least twenty carbon atoms; and a: represents a whole number I from -1 to 4.

2. As a new composition of matter, a condensation product having the general formula:

in which n represents the, number of sulphur atoms and isa whole number from 1 to 4; OZ 0001-! represents an oxy-aliphatic carboxylic acid group in which Z is an aliphatic group; R and R represent aliphatic hydrocarbon groups containing at least twenty carbon atoms: and 1: represents a whole number from 1 to 4.

3. As a new composition Ofmatter, a condensation product havingi the general formula:

in which n represents the number of sulphur atoms and is a whole number from i to 4;

O-Z-COOH represents an oxy-aromatic carboxylic acid group in which Z is an aromatic group; R and R represent aliphatic hydrocarbon groups containing at least twenty carbon atoms; 'and :1: represents a whole number from 1 to 4.

4. As a new composition of matter, a condensation product having the general formula:

in whichrn represents the number of sulphur atoms and is a whole number from 1 to 4; O-Z-COOH represents an oxy-aliphatic carboxylic acid group in-which Z is an aliphatic group; R and R represent alkyl substituents having at least twenty carbon atoms and derived from paraflln wax; and 2: represents a whole number from 1 to 4. r

5.. As a new composition of matter, a condensation product having the general formula:

an (sight). I

I I 2,881,854 in which n represents thenumber of sulphur atoms and is a whole number from 1 to 4;

-Z'-COOH represents an ,oxy-aromatic carboxylic acid group in which Zis an aromatic-group;

' R and R represent alkyl substituents having at least twenty carbon atoms and derived from paraflln' wax; and 2 represents a whole number from 1 to 4.

6. As a new composition of matter, a-condensation product characterized by at least two aryl nuclei interconnected by at least one atom of sulphur, each of said aryl nuclei being substituted with: (a) at least one alkyl substituent, a carbon atom of which is directly connected to a nuclear carbon atom of one of said aryl nuclei; and (b) at least one oxy-organic carboxylic acid group, the oxygen atom or said oxy-organic carboxylic in which n represents the number of sulphur atoms and is a whole number from 1 to 4; O-Z-CQOH-represents an oxy-org'an'ic carboxylic acidgroup in which Z is selected from the group or organic groups consisting of aliphatic, alicyclic and aromatic groups; R and R represent alkyl substituents having at least twenty carbon atoms .and derived from paraflln wax; and :1: represents a whole number from 1 to 4.

' 10. As a new composition of matter, a diiwaxphenyl, oxy-acetic acid) disulphide in which the disulphide group Joins the two wax-phenyl groups at nuclear carbon atoms thereofand in which each wax-phenyl group is attached at a nuclear carbon atom to an on? group which is also at-' tached to an acetic acid group, the said wax acid group being directly connected to a nuclear one oxy-organic carboxylic acid group, the oxygen atom of said oxy-organic carboxylic acid group being directly connected to a nuclear carbon atom of one of said aryl nuclei.

8. As a new compositionof matter, a condensation product characterized by at least two aryl nuclei interconnected by at least one atom of' sulphur, each of said aryl nuclei being substituted with: (a) at least one alkyl substituent having at least twenty carbon atoms and derived from groups'having at least twenty carbon atoms and derived from paraflin wax.

11. As anew composition oi matter, a di(wax 1 phenyl, oxy-benzoic acid) disulphide in which the disulphide grou joins the two wax-phenyl groups I at nuclear carbon atoms thereof and in which each wax-phenyl group is attached at anuclear carbon atom to an oxy group which is also attached to abenzoic acid group, they said wax groups having at least twenty carbon atoms and derived from paramn wax.

12. As a new composition of matter, an inti- "mate mixture of condensation products characs terized by at least two aryl nuclei interconnected by at least one atom of sulphur, each of said aryl nuclei' being substituted with: (a) at least parailin wax, a carbon atom of which is directly connected to anuclear carbon atom of one or said aryl nuclei; and (b) at least one oxy-organic carboxylic acid group,.the oxygen atom or said oxy-organic carboxylic acid group being directly connected to a nuclear carbon atom of one of said aryl nuclei.

9. As a new composition or I (a sag-(3').

- to thealkyl substituent, the said alkyl substitv 0 matter, a condensation product having the general formula:

one albl substituent, a carbon atom of which is directly connected to a nuclear carbon atom of one of said aryl nuclei; and (b) at least one oxy-organic carboxylic acid group, the oxygen atom of said oxy-organic carboxylic acid group being directly connected to a nuclear carbonatom of one of said aryl nuclei; the said condensation products diflering vfrom each other with respect uents comprising essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the different aliphatic hydrocarbons contained in parailln wax.

ORLAND in. REIFF. 

